ArcAaeomp/rj 33. 2 (1991), 255-266.

Printed in Great Britain

CLASSIFICATION OF FIFTEENTH- T O NINETEENTH-CENTURY

MORTARS FROM GAB11 USING INSTRUMENTAL
NEUTRON ACTIVATION ANALYSIS

G . C A P A N N E S I , C . S E C C A R O N I , A. F. S E D D A
Anal~ticulChemistry Laboratory, Chemistry Dizision, National Conimittee jor Nuclcur und Alrrrnurit~eEnergies
Research and Detielopnient, C R E Casuccia E N E A , 00060 Rome, Italy

V. M A J E R I N I and S . M U S C O
Soi.rin/endenza Archrologicu di Ronto, Piazzale delle Finunzc I , 00100 Ronie, IIal!

INTRODUCTION

The samples of mortar studied come from the farmstead of Castiglione, a rural dwelling built
in the late medieval period and located inside the archaeological site of Gabii (Rome). This
territory is historically one of the most significant among the suburban districts and was
acquired in 1987 by the Minister0 dei Beni Cultural1 e Ambientali and surrendered to the
Sovrintendenza Archeologica di Roma to form an archaeological park.
The site is located 20 km east of Rome, between the Aniene river and the hills of Albano,
along the line of the ancient Via Prenestina. Here, in the late eighth century BC grew the
Latin town of Gabii, one of the most important centres of Latium Vetus in the pre-Roman
age, later to become a Roman municipium (Guaitoli 1981, 23-57). After the end of the
classical age, even though it declined, the ancient centre remained, perhaps retaining an
important role in the administrative ecclesiastical structure of the country near Rome
because it sheltered the See of the Diocese of Gabii which, around 1060, was united with the
Diocese of Preneste (Tomassetti 1913, 580-7).
The abandonment of the ancient town site and the birth of a fortified village date back to
the twelfth and thirteenth centuries. This village is known in the sources as Castrum
Castillionis or Castrum Sanctae Praxedis from the name of the roman church that was in
possession of this district (Tomassetti and Cupis 191 1, 462).
The castrum was on the top of a hill ( 1 00 m above sea level), north of the ancient town and
built mainly with the scoriae from a neighbouring and large group of Gabii stone quarries
dated to the Roman period (Guaitoli and Piccaretta 1987, 193-200). The castrum survived
until the first years of the fifteenth century: in 1401 a papal bull of Bonifacio IX ordered the
dismantling of the fortification and the reduction of the castrum to a simple rural structure.
Now on the site, in addition to the farmstead, it is possible to observe the tower of
Castiglione that originally was a component of the same castrum and survived it. Recent
excavations have been conducted by the Sovrintendenza Archeologica di Roma on the
farmstead of Castiglione. The structure appears to have been built on the remains of the
medieval castrum and presents an L-shaped plan consisting of five building works (I-V)
carried out in that order. All the buildings have traces of numerous rebuildings that testify to
an extended use and complicated construction phases.
255
Second pha\e B Window post
C Plugging o f window
D Portal jambs
F Repairs
H (''I Threshold
L ('!) P!ugging of brick

Third phase E 5 Stifening pillars

I 1 Anomalous stiffcning pillar

(''1 unccrtaint) 111 hiiildtng pha\e artrtbutioii

The samples of mortar studied here come from building 11. from the inside of room
number 2d (see Table 1). In the last phase of use the lower floor was redesigned as a stable and
the upper floor (room number 2d) as a straw-loft or warehouse. Formerly the upper floor
was used for a lodging for seasonal farm-labourers. For building TI it is possible to
distinguish three main construction phases.
( 1 ) construction of the building, leaning against the pre-existing structure;
(2) plugging of some windows of the lower floor, of one window of the upper floor and the
reduction of the remaining windows of the upper floor;
(3) reconstruction of the roof and strengthening of the pillars that support it inside room
number 2d.
However, i t is not possible to define accurately the absolute chronology of the construction
phases. It is probable that the first phase should be placed between the end of the fifteenth
century and the first years of the sixteenth century. while the third phase is dated to around
the second half of the nineteenth century.
The samples of mortar considered come from building works related to all three
construction phases. that is first phase: original structure and arches, lintel (21 samples);
second phase: plugging of brick, window posts. plugging of windows. portal jambs, repairs,
threshold (23 samples): third phase: stiffening pillars (6 samples).

EXPERIM E S T 4 L PROCEDURES

A few specific regions belonging to different architectonic elements of the inner-side

perimeter of the room were chosen and classified by visual examination. For each region a
sample of mortar. about 8-10 cm3in volume. was withdrawn, after removing the outer crust,
using hard wood tools in order to avoid metal contamination: a total of 50 samples was
taken. The samples were made homogeneous by mild grinding in smooth glass mortars.
 Cluss@ztion of morturs,from Gabii using I N A A 257

Table 2 Analytical data obtained on u certified reference

material (SRM 688 NBS]

Element Certified (ppm) Present work (ppni)

AS 2.68 2.9i0.3
Ba 2 10 199+ 15
Ce 10.1 9.6k0.2
co 55.6 54.4 f 1 .o
Cr 329 336+15
cs 210 232 i20
Eu 1.01 0.97 k0.05
FeX, 7.23 7.12 0.1

An aliquot part of each ground mortar, about 0.5 gr, was placed in a plastic vial and
irradiated for about 30 hours in the rotating rack (Lazy Susan) of the 1 Mw TRIGA reactor
of the Institute of Casaccia with thermal neutron flux of 2.6 10l2 n cm- s- and flux
homogeneity better than 99.85%. Primary and secondary analytical standards (argillaceous
limestone SRM IC NBS, dolomite limestone SRM 88A NBS, basalt rock SRM 688 NBS)
with the same geometry as the samples were simultaneously irradiated and used for gamma
spectra calibration and conversion to concentration units.
In Table 2 are reported as a quality check the results obtained in the present work in the
analysis of a certified reference material (basalt rock SRM 688 NBS). In the sample analysis
were included only those elements whose precision, calculated by Curries method, was
better than 5% (Currie 1968).
After irradiation, the samples were allowed to decay for some days before being
transferred to the counting system. Data collection was performed using an Ortec HPGe
detector with FWHM of 1.68 keV and efficiency of 29% at 1332 keV, coupled with a Livius
(Silena) 8K channels PHA-MCA system and the net area of gamma peaks was measured.
After correction of the spectra for low-energy gamma rays attenuation due to the self
absorption of the sample, and deconvolution of the multiplets of gamma peaks, the
elements concentrations in the mortars were evaluated by direct comparison with the
irradiated primary and secondary analytical standards. A total of 19 elements was
determined. Soon afterwards every irradiated sample was treated with 1 M HCI and
successively vacuum filtered. This procedure allowed a separation of the calcareous soluble
fraction from the insoluble pozzolana and sand. Insoluble fractions were weighed and the
gamma spectrum of both of them recorded. Due to the elapsed time the activity of short half-
life isotopes decayed, and only long half-life isotopes could be determined in the separated
fractions, for a total of 9 elements per sample.

DATA ANALYSIS A N D T R E A T M E N T

The elements determined were used as input to our data treatment programs in order to
obtain the main features of the results. There follows a brief background to the statistical
methods used.
Canonical discriminant analysis (CDA) is a dimension-reduction technique related to
principal component analysis and canonical correlation (Kshirsagar 1972; Hand 198 I ;
258 G. Cupuntiesi, C. Src,curoni, A . F. Seddu, V. Mqjerini m d S. Musco

Cooley and Lohnes 1971). Given two or more groups of observations with measurements on
several quantitative variables. canonical discriminant analysis derives a linear combination
of the variables that has the highest possible multiple correlation with the groups (Fisher
1936: SAS Institute Inc. 1985). This maximal multiple correlation is called the first canonical
correlation. The coefficients of the linear combination are the canonical coefficients or
canonical weights. The variable defined by the linear combination is the first canonical
variable or canonical component. I t is customary to normalize the canonical coefficient so
that the pooled within-group variance of the canonical variable is one.
The second canonical correlation is obtained by finding the linear combination
uncorrelated with the first canonical variable that has the highest possible multiple
correlation with the groups. The process 01 extracting canonical variables can be repeated
until the number of canonical variables equals the number of original variables or the
number of classes minus one, whichever is smaller.
The first canonical correlation is at least as large as the multiple correlation between the
groups and any of the original variables. If the original variables have high within-group
correlations. the first canonical correlation is not much greater than the largest multiple
correlation. If the original variables have high within-group correlations, the first canonical
correlation can be large even if all the multiple correlations are small. In other words, the first
canonical variable can show substantial differences among the classes even if none of the
original variables do.
The following steps are sequentially performed: transform the variables so that the pooled
within-class covariance matrix is an identity matrix; compute class means on the
transformed variables; do a principal component analysis on the means, weighting each
mean by the number of observations in the class - the eigenvalues are equal to the ratio of
between-class variation to within-class in the direction of each principal component; back-
transform the principal components into the space of the original variables, obtaining the
canonical variables (CANI, CAN2. . . . CAN-n). All calculations were performed by the
SASiSTATISTICS software package (SAS Institute Inc. 1985).

RESULTS .4ND DISCUSSION

Table 1 summarizes the initial classification by visual examination of our samples, divided by
sets according to their provenance and supposed appurtenance to different building phases.
Figure 1 shows the results of CDA performed on the 50 different samples, classified by set,
using as input variables the concentrations of the 19 elements determined in the untreated
mortars. Evident is the separation of one sample of the stiffening pillars (sample I),
attributed to the third building phase, along CANI, of sample H (threshold) and sample L
(plugging of brick) along CAN3. and set E (stiffening pillars, five samples) along CAN2.
Figure 2 refers to CDA performed over all the sets by using as input variables the nine
elements determined. after separation, in the acid-soluble fraction of mortars. In this case,
the anomalous sample I is clearly reattributed to its proper set E (stiffening pillars). in
agreement with the visual classification, and the separation of the threshold (sample H) is
confirmed.
Figure 3 is the same as Figure 2, but the input variables used are the elements
concentrations in the HCI insoluble fraction of the mortars. As i n Figure 2 set E and sample I
 ClassiJicntion of mortars from Gabii using INAA 259

A
-9.5 - A A *
A
(a)
A

-3 -1 1 3 5
CAN3

-9.5 - A* * (C)
A

Figure I Canonical discriminant analysis ( C D A )performed on the 50 samples. divided by set according to Table I ;
the variables used as input are the Ba, Ce, Co. Cr, Cs. Eu, Fe, Hf; Lu, Nb, Nd, Rb, Sc, Sr. Ta, Th, Yb, Zn und Z r
concentrations in untreated mortars; C A N I . CANZ, CAN3 refer to the three main canonical variables (see t e x t ) .

are grouped together, and sample H is clearly discriminated. In Figures 2 and 3 set B
(window posts), set C (pluggings of windows) and set D (portal jambs) are grouped together.
All three sets, particularly set F, constitute (according to the visual classification) the second
260 G. Capannesi, C. Seccaroni, A . F. Sedda, V. Majerini and S. Musco
cI\1
a 2.c: - ft

e5-
A

-4.2: -1.75 2.75 5.cc

,
7
I.- c -

1 3 5
clv3

SET: A B C D E F G H I L

Figure 2 C D A perfornied on the 50 suniples, using as input rariables the Ce, Co, Cs, Eu, Fe, Sc, Sr. Tb and TI1
concentrutions in the HCI soluble fraction of niorturs.

building phase. It should be noted at this point that CDA performed by using data coming
from untreated mortars and the one from separated fractions have different and
complementary informative power.
 Class$cation of mortars from Gabii using INAA 26 1

i
I
-35 7
fr
I
-50 \ 1
1 I
-4.00 -1.25 1.50 4.25 7.00
CAN2.

CN2

"01
4.25

-5.0 -1.5 2.0 5.5 9.0

CAN3

-35 - * (C)

Figure 3 CDA performed on the 50 samples, using as input cariables the Ce, Co. Cs. Eu, Fe. Sc, Sr, Tb and T11
concentrations in the HCI insoluble fraction of mortars.

Let us now look at Table 3. Table 3(a) shows mean values of the elements concentration in
the insoluble fraction of mortars (mainly pozzolana), defined as A:/M, where A ; is the
amount of element x in the insoluble fraction and M the mass of the untreated sample. The
mutual concentration ratios among Ce, Eu and Sc are similar to the ones generally found in
262 G. Cupannesi, C. Seccaroni, A . F. Seddu, V . Mujerini and S. Musro
CAV 1

-<'O
-20
I4 *
-:c :C 20 3c
3u2

%V 2
33 1 *
20 -1
!

*
-20
-30
I
li I
A AAA A
I
(C)
i
-5.c -2.5 0.c 2.5 5.0
3Au5

nature. while Tb concentration appears two orders of magnitude lower. The pozzolana is
well known to have a relatively high content of Fe and of associated Th and Sc, and this fact
is confirmed in our results.
 Classification of mortars from Gahii using I N A A 263

It is clearly visible from Table 3(b) that in the acid soluble fraction Ce, Cs, Sr and Eu
concentrations (defined as A:/M, where A: is the amount of element x in the soluble fraction
and M the mass of the untreated sample) are higher than in the insoluble one, while Fe, Th
and Sc contents are much lower. The enrichment of Cs and Sr in the soluble, calcium-rich
fraction is forseeable. By instance, the increase of europium content can be explained by the
anomalous behaviour of Eu2+ which, among the lanthanides, presents the particularity of
replacing cations like K + or Sr2+in the crystalline lattice. Cerium is also known to present
strong concentration anomalies due to the formation of the less soluble and more easily
hydrolyzable Ce4+.
We can write the following equation

A:/M=(A:/M)+(A:/M)
where A: is the amount of element x in the total sample of mass M , A: and A: the amount of
element x in the insoluble and soluble fraction of mortars respectively. As a result the
concentrations of Table 3(c) are equal to the sum of the values of Table 3(a) and those of
Table 3(b).
The analysis of the untreated samples so furnishes information on total composition, and
not only is the elemental composition of the raw materials taken into account, but also the
little different ratios of components (i.e. lime/pozzolana ratio) are implicit discrimination
variables. The drawback of such a characteristic lies in the fact that an anomalous
component ratio can alter the analytical results of the untreated sample. On the other hand,
the composition of both acid soluble and insoluble fractions, being normalized to their
respective unit weight, is only indicative of the composition of the raw materials, irrespective
of their ratio in the mortars.
For instance, sample I is classified as a discrete entity by using discriminant analysis on
untreated mortars data, but conversely it is correctly classified as belonging to set E using
separated fraction data. The explanation of this disagreement lies in the fact that for this
sample the amount of insoluble fraction is anomalously higher than in the other samples of
the same set. The mean ratio pozzolana/lime is in fact in our samples 2.27 0.3, while for
sample I this value increases to 3.61. Due to this anomalous ratio the total composition
appears itself anomalous, even if none of the component raw materials do.
After taking all these facts into consideration we have finally tried a different combination
of variables in our CDA. Both the elements determined in the HCl soluble and insoluble
fractions of the mortars (two groups of 9 elements) and the elements of the untreated mortars
not determinable after separation (1 1 elements) were used in a new CDA run, so obtaining a
new set of 29 variables, which gave the results reported in Figure 4. The separation in the
three building phases is quite good and, for instance in CANl-CAN3 plane, virtually
unambiguous. Figure 5 is a three-dimensional representation and summarizes the three
projections of Figures 4(a), 4(b) and 4(c).
It should be noted that almost all the attributions of the building phases made on the basis
of structural and archaeological information are confirmed from our analysis, with the
exception of sample L (plugging of brick), attributed to the second building phase, of sample
H (threshold), attributed to the first building phase, and of one sample of set A, included in
the second phase.
In order to check the method response we have also performed a transposition of the data
to the principal components space. Only the first three principal components were taken into
264 G. Cupunriesi, C. Seccurwii. A . F. Seddu. I/. Mujerini und S. Musco

Element Elenimt

Ce 71.06+ 10.58 (c) Ba 1995.12 f401.08

C0 15.82i2.33 Ce 236.33f42.80
Cs 9.43 f 2.29 co 22.82k4.42
Eu 1.64i0.32 Cr 43.31 k25.31
Fe 34006.58 i 5741.98 CS 37.14k 5.46
sc 1 2 . 5 2 12.83 Eu 3.52k0.58
Sr 2044. I5 k I I 18.46 Fe 48632.58 k 8284.63
Tb 0.02 20.006 Hf 9.59 & 1.88
Th 65.502 10.53 Lu 0.002 &0.0005
Nb 0.25 k0.07
Ce 165.34k92.43 Nd 15.80f3.88
co
CS
1.92 k 4.67
14.86k 12.47
Rb
sc
*
435.88 59.34
13.09k2.88
Eu 2.14-t 1.08 Sr 8309.57f 3280.56
Fe 14718.2Sk 7372.26 Ta 0.66 k 0.26
sc I .30 i0.70 Th 67.60+ 15.04
Sr *
5975.17 3009.35 Yh 5.26k0.79
Tb 0.01520.007 Zn 42.68 33.63
Th 1.80k2.28 Zr 6.09 t I .96

4.79
 CIassiJicationof mortars from Gabii using INAA 265

0.4

0.3

SP
0.2

0.1.

I
r I I

0.0.

SET
Figure 6 Binary tree diagram obtained by cluster analysis of the analytical data transposed in the principal
components space; S P is the ratio (between cluster sum ofsquares)/(totalsum of squares) and is reported versus set of
attribution.

consideration and explained about 90% of the total group variance. A cluster analysis was
sequentially performed on the space of the principal components, using Wards minimum
variance method. The results obtained are presented in the form of a binary tree diagram in
Figure 6 . On the ordinate scale is the ratio (between cluster sum of squares)/(total sum of
squares) versus attribution set. With the exception of two samples (one sample of set A and
one of set F), the canonical discrimination analysis classification is confirmed from cluster
analysis. The total discriminant capability and the agreement of the two methods can be
considered in general quite satisfactory.

CONCLUSIONS

In this paper we have shown how some mortar samples from different periods and building
phases can be classified on the basis of elemental chemical determinations. Instrumental
neutron activation analysis appears particularly suitable in this field, due to its unique ability
in multi-elemental, non-destructive analysis coupled with high sensitivity and accuracy.
Canonical discriminant analysis, principal components analysis, clustering methods were
266 G. C'iipannesi, C. Seccaroni. A . F. Sedda, V. Mujerini and S. Musco

used in data treatment in order to obtain the maximum of information and discrimination
capability.
The final results show a completely consistent confirmation of attributions based on
archaeological and architectonic data, so proving the important role of this high-
performance analytical tool in the problems of restoration and classification.

R E F :E R E N C ES

Cook!. W. W. and Lohnes. P. R.. 1971. rMid/ii.uriui~~ ciura utia/>..sis.John Wiley and Sons, New York.
C'urrie. L. A. 1968. Limits for quantitative detection and quantitative determination, Anal. Chem., 40, 586 93.
Fisher. R . A . . 1936. The use of multiple measurement in taxonomic problems. Annuls of Eugenics, 7, 179-88.
Guaitoli, M . 198 I . Gabii: osservazioni sulle fasi di s\ iluppo dell'abitato. Quaderni riell'lrisriruro di Topogrufia di
Ronrtr 6' ~ l ~ ~ l l ' l i u, Al rt iut r c u dell'.L'tiirersiru' di Rorncr 1. 9. 13- 57.
Guaitoli. M . and Piccaretta. F.. 1987. Manumle tfi,/orogrufiuuereu: uso arcliaeologico, 193-200, Rome.
Hand. D. 3 . . 1981. Discrirninrriiori and c/ass(ficuriorr. John Wiley and Sons. New York.
Kshirsapar. A . M.. 1972. .Mulrirtrriute utia/I.si.s. Marcel Dekker. New York.
SAS Institute Inc.. 1985. S A S user'., guide: .srarisrics, rer.rion 5 edition, Cary. New York.
Tomassetti. G.. 19 13, Lu cunipugncr Ronrartu aiiticci, viedrei.rrlr e nioderna. Rome.
Tomassetti. M. and Cupis. C. de. 1911, Le ricetide (le11'agric~olruruc deNa pastoriziu nell'Agro Romano, Rome,

Conference Announcements

1 Y92: INTERNATIONAL ARCHAEOMETRY SYMPOSIUM: 23-27 March, Los

Angeles
Contact: Dr Pieter Meyers, Los Angeles County Museum of Art, 5905 Wilshire
Boulek ard, Los Angeles, California 90036. USA
1992: TENTH INTERNATIONAL CONFERENCE ON SOLID STATE DOSI-
METRY: 13-1 7 July, Washington DC
Contact: Dr S. W. S. McKeever, 10th SSD Conference, Department of Physics,
Oklahoma State University, Stillwater. OK 74075. USA